2008 Vol. 21, No. 5

Xenon atoms were produced in their metastable states 5p56s[3/2]2 and 5p56s′[1/2]0 in a pulsed DC discharge in beam,and subsequently excited to the even-parity autoionizing Rydberg states 5p5np′[3/2]1,[1/2]1,and 5p5nf′ [5/2]3 using single photon excitation. The excitation spectra of the even-parity autoionizing resonance series from the metastable 129Xe were obtained by recording the autoionized Xe+ with time-of-flight ion detection in the photon energy range of 28000-42000cm-1 .A wealth of autoionizing resonances were newly observed, from which more precise and systematic spectroscopic data of the level energies and quantum defects were derived.
The rate constants of the reaction between hydroxyl radical (OH?) and dimethyl sulfide (DMS) were in-vestigated by using the relative methods in air, N2, and O2. Strong influences of ground state oxygenO(3P) on DMS consumption were found by the photolysis of HONO and CH3ONO as OH?sources, and the rate constants obtained in these systems varied significantly. The rate constants of the reaction between DMS and OH?(generated by photolysis of H2O2) at room temperature were 8.56×10-12, 11.31×10-12, and 4.50×10-12cm3/(molecule?s), in air, O2, and N2, respectively. The temperature dependence of the rateconstants for OH? with DMS over the temperature range of 287-338 K was also investigated in nitrogen and air, and the Arrhenius expression was obtained as follows: kair=(7.24±0.28)×10-13exp[(770.7±97.2)/T],kN2=(3.40±0.15)×10-11exp[-(590.3±165.9)/T].
The absorption spectra of acetylene molecules was measured under jet-cooled conditions in the wavelength range of 142.8-152.3 nm,with a tunable and highly resolved vacuum ultraviolet (VUV) laser generated by two-photon resonant four wave difference frequency mixing processes. Due to the sufficient vibrational and rotational cooling effect of the molecular beam and the higher resolution VUV laser, the observed absorption spectra exhibit more distinct spectral features than the previous works measured at room temperature. The major three vibrational bands are assigned as a C{C symmetry stretching vibrational progress (v2=0-2) of the C1Ⅱu state of acetylene.The observed shoulder peak at 148.2 nm is assigned to the first overtone band of the trans-bending mode v4 of the C1Ⅱu state of acetylene. Additionally,the two components, 420 (μ1Ⅱu) and 420(к1Ⅱu),are suggested to exhibit in the present absorption spectra,due to their Renner-Teller effect and transition selection rule.All band origins and bandwidths are obtained subsequently,and it is foundthat bandwidths are broadened and lifetimes decrease gradually with the excitation of vibration.
Dynamic alignment of D2 induced by two few-cycle pulses was investigated by solving the time-dependent Schr?odinger equation numerically based on a rigid rotor model. The results show that alignment of D2 can be enhanced by two few-cycle pulses compared with the level achievable by a single few-cycle pulse as long as the time delay between two pulses is chosen properly, and the pulse duration of two lasers plays an important role in the aligning process of D2 molecules.
A novel analysis approach using atomic fluorescence excited by synchrotron radiation is presented.A system for synchrotron radiation-atomic fluorescence spectrometry is developed, and experimental conditions such as flow rate, analyte acidity, concentration of pre-reducing and hydrogenation system are optimized. The proposed method is successfully applied to get an excitation spectrum of arsenic. Seven of ten primary spectral lines, four of which have never been reported by means of atomic fluorescence spectrometry, agree well with the existing reports.The other three are proposed for the first time. Excitation potentials and possible transitions are investigated. Especially for the prominent line at 234.99 nm, the mechanism of generation is discussed and a model of energy transition processes is proposed.
During the measurement of atmospheric nitrate radical by long-path differential optical absorption spectroscopy, water vapor strong absorption could affect the measurement of nitrate radical and detection limits of system. Under the tropospheric condition, the optical density of water vapor absorption is non-linearly dependent on column density. An effective method was developed to eliminate the effect of water vapor absorption. Reference spectra of water vapor based on the daytime atmospheric absorption spectra, when fitted together with change of cross section with water vapor column densities, gave a more accurate fitting of water vapor absorptions, thus its effect on the measurements of nitrate radical could be restricted to a minimum and detection limits of system reached 3.6 ppt. The modified method was applied during an intensive field campaign in the Pearl River Delta, China. The NO3 concentration in polluted air masses varied from 3.6 ppt to 82.5 ppt with an average level of 23.6±1.8 ppt.
To study the Fe?M interactions and their effects on 31P NMR, the structures of Fe(CO)3(EtPhPpy)2 1,Fe(CO)3(EtPhPpy)2M(NCS)2 (2: M=Zn, 3: M=Cd, 4: M=Hg) and Fe(CO)3(EtPhPpy)2CdX2 (5: X=Cl,6: X=SCN) were investigated by density functional theory (DFT) PBE0 method. The stabilities S of complexes follow S(2)>S(3)>S(4) and S(3)≈S(6)>S(5), indicating that 6 is stable and may be synthesized.The complexes with thiocyanate are more stable than that with chloride in Fe(CO)3(EtPhPpy)2CdX2.The strength I of Fe-M interactions follows I(2)≈I(3)
Using density functional theory with generalized gradient approximation and hybrid functional, we studied the properties of energy, charge population, and vibration of CH2 and CH3 adsorbed on Cun (n=1-6) clusters. The results show that the DFT calculation with the hybrid functional matches the experimental results better in both cases. The calculation results indicate that the adsorption of CH2 is stronger than that of CH3. During adsorption, the charges transfer from Cu to CH2 or CH3. The obtained vibrational frequencies for different modes of CH2 and CH3 adsorbed on Cun agree well with the experimental results for the adsorption on Cu(111) surface.
It was investigated that the domain growth processes of spinodal decomposition with different quenching depth in two and three dimensional binary immiscible fluids by using parallel dissipative particle dynamics simulations. In two dimensions, the dynamic scaling exponent 1/2 for coalescence and 2/3 for inertial regimes in the shallow quench and strong finite size effects in the cases of deep quenching were obtained. In three dimensions, it was used that the diffusive regime with exponent n=1/3 in the shallow quench and the inertial hydrodynamic regime with n=2/3 for different quenches. The viscous effects are not clearly reflected, showing n=1/2 in both shallow and deep quenches in this time period, due to the soft nature of interaction potential adopted in dissipative particle dynamics.
As a further theoretical study of the collision-induced quantum interference on rotational energy transfer in an atom-diatom system, based on the first-Born approximation of time-dependent perturbation theory, taking into account the anisotropic Lennard-Jones interaction potential and the long-range interaction potential, the differential interference angles in singlet-triplet mixed states of CO A1Ⅱ(v=0)~e3∑-(v=1)system in collision with He, Ne, Ar, and other partners were calculated theoretically. The relationships of differential interference angle versus impact parameters, including collision parameter b and velocity, are obtained.
The elastic behavior of the polymer chain was investigated in a three-dimensional off-lattice model. We sample more than 109 conformations of each kind of polymer chain by using a Monte Carlo algorithm, then analyze them with the non-Gaussian theory of rubberlike elasticity, and end with a statistical study. Through observing the effect of the chain flexibility and the stretching ratio on the mean-square end-to-end distance, the average energy, the average Helmholtz free energy, the elastic force, the contribution of energy to the elastic force, and the entropy contribution to elastic force of the polymer chain, we find that a rigid polymer chain is much easier to stretch than a flexible polymer chain. Also, a rigid polymer chain will become difficult to stretch only at a quite high stretching ratio because of the effect of the entropy contribution. These results of our simulation calculation may explain some of the macroscopic phenomena of polymer and biomacromolecular elasticity.
(2-acrylamido) ethyl tetradecyl dimethylammonium bromide (AMC14AB) was polymerized in aqueous solution to form the homopolymer P(AMC14AB). The physicochemical properties of P(AMC14AB) in aqueous solution were mainly studied with fluorescent probe method, surface tension measurement and conductometry. The experimental results show that the aggregation morphology of P(AMC14AB) in aqueous solution is unimolecular micelle as expected. Being different from conventional multimolecular micelle systems, the unimolecular micelle system of P(AMC14AB) not only shows critical micellar concentration (CMC=0), (i.e.once added to pure water, the surface tension decreases immediately in spite how small the density is), but also the surface tension stays almost the same with the concentration increasing. That is to say, there is no mutational point on the relationship curve between surface tension and concentration. Furthermore, the unimolecular micelle system of P(AMC14AB) has no Krafft temperature, i.e. at any temperature, so long as it is dissolved in water, the unimolecular micelles will form. Besides this, for the solubilization of hydrophobic organic substances, the unimolecular micelle system of P(AMC14AB) is obviously different from the common multimolecular micelle system, having no turning point on the relationship curve between toluene solubilizaion amount and P(AMC14AB) concentration, and the solubilizing ability of the unimolecular-micelle system of P(AMC14AB) for hydrophobic organic substances is much higher than that of the conventional multimolecular micelle solutions of common surfactants, such as centyl trimethyl ammonium bromide.
A plasma-assisted method was employed to prepare Ni/γ-Al2O3 catalyst for carbon dioxide reforming of methane reaction. The novel catalyst possessed higher activity and better coke-suppression performance than those of the conventional calcination catalyst. To achieve the same CH4 conversion, the conventional catalyst needed higher reaction temperature, about 50 °C higher than that of the N2 plasma-treated catalyst. After the evaluation test, the deactivation rate of the novel catalyst was 1.7%, compared with 15.2% for the conventional catalyst. Different from the characterization results of the calcined catalyst, a smaller average pore diameter and a higher specific surface area were obtained for the plasma-treated catalyst. The variations of the reduction peak temperatures and areas indicated that the catalyst reducibility was promoted by plasma assistance. The dispersion of nickel was also remarkably improved, which was helpful for controlling the ensemble size of metal atoms on the catalyst surface. The modification effect of plasmaassisted preparation on the surface property of alumina supported catalyst was speculated to account for the concentration increase of absorbed CO2. An enhancement of CO2 adsorption was propitious to the inhibition of carbon formation. The coke amount deposited on plasma treated catalyst was much smaller than that on the conventional catalyst.
Au nanorods have been successfully synthesized at 90°C by using hexadecyltrimethylammonium bromide (CTAB) and benzyldimethylammoniumchloride hydrate (BDAC) co-surfactant. At 90 °C, the reaction time was less than 10 s, and the longitudinal surface plasmon absorption band could vary between 680 and 770 nm by adjusting the molar ratio of BDAC to CTAB from 2 to 0.5. At 90 °C, nanorods with a longitudinal surface plasmon absorption peak of 770 nm can be obtained when the molar ratio of BDAC to CTAB was 3:2.
A series of Cr doped TiO2 films were prepared by micro arc oxidation (MAO) using an electrolyte of Na3PO4+K2Cr2O7. X-ray diffraction and scanning electron microscopy revealed that the films mainly consisted of anatase phase with a porous surface morphology. The films have an excellent photocatalytic effect for degradation of methylene blue and decomposition of water under visible light illumination. This arises from the formation of Cr3+/Cr4+ and oxygen vacancy energy levels owing to Cr doping. The former reduces the electron-hole recombination chance, while the latter generates a new gap between the conduction band (CB) and valence band (VB) of TiO2, which lowers the photo energy of the excited electron in the VB to the oxygen vacancy states. The mechanisms for film synthesis during the MAO process are also presented.
Three series of amorphous copolymers containing azobenzene groups with various substituents and certain amounts of crosslinkable acrylic groups were prepared. The cross-linked polymer films were obtained by thermal polymerization of the acrylic groups in the copolymers, during which, by controlling the time of cross-linking reaction, the films can be made with different cross-linking degree (from 0 to 32%, which was monitored by FT-IR spectra measurement). Photo-induced alignment process of the films was performed under irradiation with linearly polarized light at 442 nm, and the effect of cross-linking degree on the photo-induced alignment rate was investigated. The dynamics of the photo-induced alignment was analyzed with biexponential curve fitting. The photo-induced alignment rate and the maximum transmittance of the films decreased because of the cross-linking. Furthermore, for the cross-linked samples, it was found that their saturated value of transmittances keep constant after repeated "writing" and "erasing" cycles. The findings reveal that the cross-linking of the film can effectively restrain the phototactic mass transport of azopolymer during irradiation by polarized light. The relationship between the cross-linking degree and the photo-induced alignment behavior of azopolymer is discussed in detail.
White organic light-emitting diodes (WOLEDs) with a structure of indium-tin-oxide (ITO)/N,N'-bis-(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (NPB)/1,2,3,4,5,6-hexakis(9,9-diethyl-9H-fluoren-2-yl)benzene (HKEthFLYPh)/5,6,11,12 -tetraphenylnaphtacene (rubrene)/tris(8-hydroxyquinoline) aluminum (Alq3)/Mg:Ag were fabricated by vacuum deposition method, in which a novel star-shaped hexafluorenylbenzene HKEthFLYPh was used as an energy transfer layer, and an ultrathin layer of rubrene was inserted between HKEthFLYPh and Alq3 layers as a yellow light-emitting layer instead of using a time-consuming doping process. A fairly pure WOLED with Commissions Internationale De L'Eclairage (CIE) coordinates of (0.32, 0.33) was obtained when the thickness of rubrene was 0.3 nm, and the spectrum was insensitive to the applied voltage. The device yielded a maximum luminance of 4816 cd/m2 at 18 V.